Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/02—Aliphatic polycarbonates
  • C08G64/0208—Aliphatic polycarbonates saturated
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
  • C07F13/005—Compounds without a metal-carbon linkage
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/22—Catalysts containing metal compounds
  • C08G18/24—Catalysts containing metal compounds of tin
  • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
  • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/44—Polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
  • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
  • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/20—General preparatory processes
  • C08G64/30—General preparatory processes using carbonates
  • C08G64/305—General preparatory processes using carbonates and alcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
  • C08G71/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/06—Polyurethanes from polyesters

Definitions

• the present invention relates to a method for producing a polycarbonate diol, a polycarbonate diol and a transesterification catalyst, as well as a polyurethane in which the polycarbonate diol is used.
• Polyurethane resins and polyurea resins have been conventionally used in a wide range of fields such as synthetic leather, artificial leather, adhesives, coating materials for furniture, and coating materials for automobiles.
• Polyethers and polyesters are used as polyol components to be reacted with isocyanates (see, for example, Patent Document 1 and Non Patent Document 1).
• requirements for resistance of resins for example, heat resistance, weather resistance, hydrolysis resistance, fungal resistance, and oil resistance have been increasingly higher in recent years.
• Transesterification catalysts are usually used in production of polycarbonate diols and polyesters.
• metallic sodium is used as a catalyst in production of a copolymerized polycarbonate diol of diethyl carbonate with 1,6-hexanediol and 1,5-pentanediol (see, for example, Patent Document 6)
• sodium ethoxide and/or magnesium acetate are/is used as catalyst(s) in a combination of diethyl carbonate with a diol such as 1,3-propanediol, 2-methyl-1,3-propanediol, or 1,3-butanediol (see, for example, Patent Document 7).
• lead acetate or tetra-n-butyl titanate is used as a catalyst in production of a copolymerized polycarbonate diol of ethylene carbonate with diols such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol and 2-methyl-1,3-propanediol
• tetra-n-butyl titanate is used as a catalyst in production of a polycarbonate diol of ethylene carbonate with various alkylenediols, and oxyalkylenediols such as diethylene glycol and dibutylene glycol (see, for example, Patent Document 8).
• magnesium acetate is used as a catalyst in production of a copolymerized polycarbonate diol of diphenyl carbonate with 1,6-hexanediol and neopentyl glycol (see, for example, Patent Document 10).
• Non Patent Document 1 Katsuji Matsunaga (supervisor), ‘Basic and Application of Polyurethane’, pp. 96 to 106, CMC Publishing Co., Ltd., issued in November 2006
• titanium compounds if used as catalysts, are not sufficient in activity and therefore tend to cause a long time to be taken for production.
• a long reaction time promotes formation of undesirable ether groups and/or vinyl groups. These groups can cause losses in weather resistance and heat resistance of the resulting polyurethane in the case of use of polycarbonate diols and polyesters as starting materials for polyurethane, and therefore are not preferred as starting materials for polyurethane.
• Magnesium acetate, magnesium alkoxide and magnesium acetylacetone when used as catalysts, are high in polymerization activity to provide an improvement in productivity, as compared with titanium compounds, but do not sufficiently provide such an improvement, and therefore have room for improvement in terms of coloration of the resulting polycarbonate diol and polyester and an enhancement in productivity thereof.
• An object of the present invention is then to provide a method for efficiently (specifically, for example, under milder reaction conditions within a short time) producing a polycarbonate diol. Another object thereof is to provide a polycarbonate diol excellent in color tone, small in ether linkage and high in terminal primary hydroxyl group (OH) purity, and a polyurethane in which the polycarbonate diol is used and which is excellent in chemical resistance, heat resistance, and hydrolysis resistance. Another object of the present invention is to provide a highly active catalyst for efficiently (specifically, for example, under milder reaction conditions within a short time) producing a polycarbonate diol or a polyester.
• the present inventor has made intensive studies in order to solve the problems, and as a result, has found that a polycarbonate diol or a polyester can be efficiently produced by use of at least two transesterification catalysts each containing a specified metal in production of such a polycarbonate diol or a polyester with polycondensation by transesterification reaction and thus the problems can be solved.
• the inventor has also found a polycarbonate diol excellent in color tone, small in ether linkage and high in terminal primary hydroxyl group (OH) purity, and a polyurethane in which the polycarbonate diol is used and which is excellent in chemical resistance, heat resistance and hydrolysis resistance.
• the gist of the present invention is as follows.
• a method for producing a polycarbonate diol comprising a step of obtaining a polycarbonate diol with polycondensation by transesterification reaction of a dihydroxy compound and a carbonate ester as starting material monomers in the presence of a transesterification catalyst, wherein
• R 1 and R 3 each independently represent a monovalent hydrocarbon group having 1 to 10 carbon atoms, the hydrocarbon groups of R 1 and R 3 are each optionally substituted with a halogen atom or each optionally have an oxygen atom
• R 2 represents hydrogen, or a monovalent hydrocarbon group having 1 to 10 carbon atoms, the hydrocarbon group of R 2 is optionally substituted with a halogen atom or optionally has an oxygen atom
• M1 represents at least one metal selected from the group consisting of metals in Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 in the long-period type periodic table
• n is 1, 2 or 3
• the metal complex represented by the formula (1) is optionally an associated product of a plurality of such metal complexes.
• transesterification catalyst A1 corresponds to a salt of at least one carboxylic acid represented by the following formula (2) and at least one metal (M1) selected from the group consisting of metals in Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 in the long-period type periodic table, and/or a hydrate thereof:
• R 4 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group of R 4 is optionally substituted with a halogen atom or optionally has an oxygen atom.
• transesterification catalyst A2 is an alcoholate of at least one alcohol represented by the following formula (3) and at least one metal (M2) selected from the group consisting of metals in Group 1 and Group 4 in the long-period type periodic table:
• R 5 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group of R 5 is optionally substituted with a halogen atom or optionally has an oxygen atom.
• R 6 represents a divalent aliphatic or alicyclic hydrocarbon group having 2 to 20 carbon atoms.
• R represents a divalent aliphatic hydrocarbon group or alicyclic hydrocarbon group having 2 to 20 carbon atoms, and m is an integer of 2 or more and 600 or less;
• metal (M1) is at least one metal selected from the group consisting of molybdenum, manganese, iron, cobalt, nickel and copper
• metal (M2) is at least one metal selected from the group consisting of lithium, sodium, potassium, titanium, zirconium and hafnium.
• a polyurethane comprising the polycarbonate diol according to any of [12] to [15].
• a transesterification catalyst comprising at least two transesterification catalysts of a transesterification catalyst A1 containing at least one metal (M1) selected from the group consisting of metals in Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 in the long-period type periodic table and a transesterification catalyst A2 containing at least one metal (M2) selected from the group consisting of metals in Group 1 and Group 4 in the long-period type periodic table.
• M1 containing at least one metal (M1) selected from the group consisting of metals in Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 in the long-period type periodic table
• M2 containing at least one metal (M2) selected from the group consisting of metals in Group 1 and Group 4 in the long-period type periodic table.
• R 1 and R 3 each independently represent a monovalent hydrocarbon group having 1 to 10 carbon atoms, the hydrocarbon groups of R 1 and R 3 are each optionally substituted with a halogen atom or each optionally have an oxygen atom
• R 2 represents hydrogen, or a monovalent hydrocarbon group having 1 to 10 carbon atoms, the hydrocarbon group of R 2 is optionally substituted with a halogen atom or optionally has an oxygen atom
• M1 represents at least one metal selected from the group consisting of metals in Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 in the long-period type periodic table
• n is 1, 2 or 3
• the metal complex represented by the formula (1) is optionally an associated product of a plurality of such metal complexes.
• transesterification catalyst A1 corresponds to a salt of at least one carboxylic acid represented by the following formula (2) and at least one metal (M1) selected from the group consisting of metals in Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 in the long-period type periodic table, and/or a hydrate thereof:
• R 4 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group of R 4 is optionally substituted with a halogen atom or optionally has an oxygen atom.
• transesterification catalyst A2 is an alcoholate of at least one alcohol represented by the following formula (3) and at least one metal (M2) selected from the group consisting of metals in Group 1 and Group 4 in the long-period type periodic table:
• R 5 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group of R 5 is optionally substituted with a halogen atom or optionally has an oxygen atom.
• the method for producing a polycarbonate diol of the present invention can efficiently produce a polycarbonate diol or a polyester, for example, in milder conditions than those of a conventionally known technique.
• the present invention can provide a polycarbonate diol or a polyester excellent in color tone, small in ether linkage and high in terminal primary hydroxyl group (OH) purity, and a polyurethane in which the polycarbonate diol or the polyester is used and which is excellent in chemical resistance, heat resistance, and hydrolysis resistance.
• the present embodiment for carrying out the present invention is described in detail.
• the present invention is not limited to the following embodiment, and can be variously modified and carried out within the gist thereof.
• a method for producing a polycarbonate diol of the present embodiment includes a step of obtaining a polycarbonate diol with polycondensation by transesterification reaction of a dihydroxy compound and a carbonate ester as starting material monomers in the presence of a transesterification catalyst, wherein
• the method for producing a polycarbonate diol of the present embodiment can thus efficiently (specifically, for example, under milder reaction conditions within a short time) produce a polycarbonate diol by use of at least two transesterification catalysts each containing a specified metal.
• a dihydroxy compound and a carbonate ester are used as starting material monomers in the method for producing a polycarbonate diol of the present embodiment.
• dihydroxy compound serving as a starting material monomer in the method for producing a polycarbonate diol of the present embodiment can include, but not particularly limited, linear compounds each having a dihydroxy terminal, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol and 1,20-eicosanediol; ether group-containing dihydroxy compounds such as diethylene glycol, triethylene glycol, tetraethylene glycol, polypropylene glycol and polytetramethylene glycol; thioether diols such as bishydroxyethyl thioether; 2,2-
• the dihydroxy compound is preferably at least one compound selected from the group consisting of an aliphatic dihydroxy compound and an alicyclic dihydroxy compound, more preferably at least one compound selected from the group consisting of an aliphatic dihydroxy compound and an alicyclic dihydroxy compound represented by the following formula (4), from the viewpoint of weather resistance of a polyurethane obtained with the polycarbonate diol of the present embodiment:
• R 6 represents a divalent aliphatic or alicyclic hydrocarbon group having 2 to 20 carbon atoms.
• the aliphatic dihydroxy compound is particularly preferably 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 3-methyl-1,5pentanediol, or 2-methyl-1,8-octanediol, and the alicyclic dihydroxy compound is particularly preferably 1,4-cyclohexane dimethanol or tricyclodecane dimethanol.
• dihydroxy compounds may be used singly or in combinations of two or more kinds thereof depending on requirement performances of the resulting polycarbonate diol, and a copolymerized polycarbonate diol is preferred which is obtained by combining a plurality of these dihydroxy compounds.
• the copolymerized polycarbonate diol not only is generally inhibited from being crystallized, and is higher in fluidity than a homo-polycarbonate diol and is excellent in operation ability when processed into a polyurethane, but also can impart flexibility and texture to a polyurethane.
• the compositional ratio in copolymerization is preferably set so that 5% by mol or more, preferably 10% by mol or more, more preferably 20% by mol or more, further preferably 30% by mol or more of each of the dihydroxy compounds is used based on the total of the dihydroxy compounds.
• copolymerization of dihydroxy compounds different in molecular structure may cause heterogeneous polymerization reaction or inhibition of polymerization due to the difference in reactivity, but the present embodiment in which a specified transesterification catalyst described below is used can easily provide a copolymerized polycarbonate diol.
• the carbonate ester usable as a starting material monomer in the method for producing a polycarbonate diol of the present embodiment is not limited as long as the effects of the present invention are not impaired, and examples thereof include dialkyl carbonate, diaryl carbonate, or alkylene carbonate.
• diaryl carbonate examples include, but not particularly limited, diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, and di-m-cresyl carbonate.
• alkylene carbonate examples include, but not particularly limited, ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 1,3-pentylene carbonate, 1,4-pentylene carbonate, 1,5-pentylene carbonate, 2,3-pentylene carbonate, 2,4-pentylene carbonate, and neopentyl carbonate.
• dimethyl carbonate, diethyl carbonate, ethylene carbonate, and diphenyl carbonate are particularly preferred which are inexpensively available as industrial starting materials, are good in reactivity, and cause a small amount of alcohols as by-products.
• the amount of the carbonate ester used in the method for producing a polycarbonate diol of the present embodiment is needed to be appropriately changed depending on an objective molecular weight of the polycarbonate diol, and is not particularly limited, and the lower limit is usually preferably 0.5, more preferably 0.7, further preferably 0.8, and the upper limit is usually 1.5, preferably 1.3, more preferably 1.2, on the molar ratio based on 1 mol in total of these dihydroxy compounds.
• the amount of the carbonate ester used is equal to or less than the upper limit, the proportion of one in which the terminal group of the resulting polycarbonate diol is not a hydroxyl group can be suppressed, or the polycarbonate diol of the present embodiment, in which the molecular weight is within a predetermined range, tends to be able to be produced, and when the amount is equal to or more than the lower limit, polymerization tends to progress until a predetermined molecular weight is achieved.
• the transesterification catalyst used in the present embodiment includes at least two transesterification catalysts of a transesterification catalyst A1 containing at least one metal (M1) selected from the group consisting of metals in Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 in the long-period type periodic table and a transesterification catalyst A2 containing at least one metal (M2) selected from the group consisting of metals in Group 1 and Group 4 in the long-period type periodic table.
• M1 containing at least one metal (M1) selected from the group consisting of metals in Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 in the long-period type periodic table
• M2 containing at least one metal (M2) selected from the group consisting of metals in Group 1 and Group 4 in the long-period type periodic table.
• One mode of the transesterification catalyst A1 containing at least one metal (M1) selected from the group consisting of metals in Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 in the long-period type periodic table is preferably at least one metal complex represented by the following formula (1) and/or a hydrate thereof:
• a ligand to the metal in the metal complex represented by the formula (1) is an acetylacetone analog, and can be represented as a form in which a negative ion is not localized, as represented by the following formula (7), or can also be represented again as a form in which three organic anions are in an equilibrium state, as represented by the following formula (8):
• Examples of the method for preparing the transesterification catalyst represented by the formula (1) include a method for preparing the transesterification catalyst represented by the formula (1) by allowing a metal halide and an acetylacetone analog to act in the presence of a base, as represented by the following formula (9), and a method for preparing the transesterification catalyst represented by the formula (1) by exchange between a metal alkoxide and an acetylacetone analog, as represented by the following formula (10), but not limited thereto:
• R 1 , R 2 , R 3 , M1 and n are as defined in the formula (1), X represents any halogen atom, and R 8 represents any hydrocarbon group.
• the transesterification catalyst represented by the formula (1) can be used accessorily in combination with a transition metal compound, or a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine-based compound.
• R 1 and R 3 in the formula (1) include, but not particularly limited, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a cyclohexyl group, a phenyl group, a benzyl group, a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a monochloromethyl group, a dichloromethyl group, and a trichloromethyl group, and among them, in particular, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, and
• R 2 include, but not particularly limited, hydrogen, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a cyclohexyl group, a phenyl group, a benzyl group, a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a monochloromethyl group, a dichloromethyl group, a trichloromethyl group, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among them, hydrogen, a methyl group, an ethyl group, a n-propyl group, an iso
• the metal (M1) selected from the group consisting of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 in the long-period type periodic table is not particularly limited, molybdenum, manganese, iron, cobalt, nickel and copper are preferred from the viewpoint of catalyst activity, and among them, manganese is particularly preferred.
• An organometal complex with such an acetylacetone analog, used in the transesterification catalyst of the present embodiment, can also be used in the form of a hydrate.
• transesterification catalyst A1 containing at least one metal (M1) selected from the group consisting of metals in Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 in the long-period type periodic table is preferably a salt of at least one carboxylic acid represented by the following formula (2) and at least one metal (M1) selected from the group consisting of metals in Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 in the long-period type periodic table, and/or a hydrate thereof:
• R 4 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group of R 4 is optionally substituted with a halogen atom or optionally has an oxygen atom.
• carboxylic acid examples include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, palmitic acid, margaric acid, and stearic acid, and among them, acetic acid, propionic acid, and butyric acid are preferred, and acetic acid is particularly preferred.
• the metal (M1) selected from the group consisting of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 in the long-period type periodic table is not particularly limited, molybdenum, manganese, iron, cobalt, nickel and copper are preferred from the viewpoint of catalyst activity, and among them, manganese is particularly preferred.
• the salt of such a carboxylic acid, used in the transesterification catalyst of the present embodiment, can also be used in the form of a hydrate.
• the transesterification catalyst used in the present embodiment includes at least two transesterification catalysts of the above transesterification catalyst A1 and a transesterification catalyst A2 containing at least one metal (M2) selected from the group consisting of metals in Group 1 and Group 4 in the long-period type periodic table.
• Examples of the metals in Group 1 in the long-period type periodic table include, but not particularly limited, lithium, sodium, potassium, rubidium, cesium, and francium.
• lithium, sodium, and potassium are high in catalyst activity and thus preferred.
• Lithium is particularly preferred which is particularly high in activity and which allows a polycarbonate diol produced to be small in amount of ether linkage.
• Examples of the metals in Group 4 in the long-period type periodic table include, but not particularly limited, titanium, zirconium, and hafnium.
• titanium is particularly preferred which is high in activity and which allows a polycarbonate diol produced to be small in amount of ether linkage.
• Examples of the mode of the transesterification catalyst A2 containing at least one metal (M2) selected from the group consisting of metals in Group 1 and Group 4 in the long-period type periodic table include, but not particularly limited, a salt with an inorganic acid, a salt with an organic acid, alcoholates of various alcohols, and hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and titanium hydroxide.
• an alcoholate of at least one alcohol represented by the following formula (3) and at least one metal (M2) selected from the group consisting of metals in Group 1 and Group 4 in the long-period type periodic table is preferred because of being high in catalyst activity and causing less coloration:
• R 5 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group of R 5 is optionally substituted with a halogen atom or optionally has an oxygen atom.
• Examples of the alcoholate of at least one alcohol and any metal in Group 1 in the long-period type periodic table, represented by the formula (3), include, but not particularly limited, lithium methylate (lithium methoxide), lithium ethylate (lithium ethoxide), lithium propoxide, lithium butoxide, sodium methylate (sodium methoxide), sodium ethylate (sodium ethoxide), sodium propoxide, sodium butoxide, potassium methylate (potassium methoxide), potassium ethylate (potassium ethoxide), potassium propoxide, potassium butoxide, rubidium methoxide, rubidium ethoxide, cesium methoxide, and cesium ethoxide.
• lithium methylate, lithium ethylate, sodium methylate, and sodium ethylate are preferred which each are high in catalyst activity and allow a polycarbonate diol produced to be small in amount of ether linkage and less colored, and lithium methylate and lithium ethylate are particularly preferred.
• Examples of the alcoholate of at least one alcohol and any metal in Group 4 in the long-period type periodic table, represented by the formula (3), include, but not particularly limited, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetra-n-butoxy zirconium, tetra-n-butoxy hafnium, tetra-t-butoxy zirconium, and tetra-t-butoxy hafnium.
• tetraisopropoxy titanium and tetra-n-butoxy titanium are preferred which each are high in catalyst activity and allow a polycarbonate diol produced to be small in amount of ether linkage and less colored.
• the transesterification catalyst used in the present embodiment includes at least two transesterification catalysts of the transesterification catalyst A1 containing at least one metal (M1) selected from the group consisting of metals in Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 in the long-period type periodic table, and the transesterification catalyst A2 containing at least one metal (M2) selected from the group consisting of metals in Group 1 and Group 4 in the long-period type periodic table.
• M1 metal selected from the group consisting of metals in Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 in the long-period type periodic table
• M2 at least one metal selected from the group consisting of metals in Group 1 and Group 4 in the long-period type periodic table
• transesterification catalyst A1 and the transesterification catalyst A2 can be used in combination, rather than single use of the transesterification catalyst A1 or the transesterification catalyst A2, thereby imparting higher catalyst activity, for example, efficiently producing a polycarbonate diol.
• the transesterification catalyst A1 containing at least one metal (M1) selected from the group consisting of metals in Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 in the long-period type periodic table is coordinated as Lewis acid to carbonyl oxygen of a carbonate group.
• M1 metal selected from the group consisting of metals in Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 in the long-period type periodic table
• the transesterification catalyst A2 containing the at least one metal M2 selected from the group consisting of metals in Group 1 and Group 4 in the long-period type periodic table is considered to allow oxygen of alcohol to be anionic, promoting reaction with activated carbonyl carbon.
• M1 represents at least one metal selected from the group consisting of metals in Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 in the long-period type periodic table
• M2 represents at least one metal selected from the group consisting of metals in Group 1 and Group 4 in the long-period type periodic table
• R 11 , R 12 , and R 13 each represent any hydrocarbon group
• Li represents any ligand (optionally represents a plurality of ligands).
• the method of using the transesterification catalyst of the present embodiment is not particularly limited, and when the transesterification catalyst is used for polycarbonate diol production, examples of the method usually include a method including subjecting the dihydroxy compound and the carbonate ester used as starting material monomers to polycondensation with transesterification reaction by addition of the transesterification catalyst of the present embodiment.
• examples of the method usually include a method including subjecting the dihydroxy compound and a dibasic acid such as adipic acid or phthalic acid and/or a methyl ester or ethyl ester compound thereof to polycondensation with transesterification reaction by addition of the transesterification catalyst of the present embodiment.
• the transesterification catalyst of the present embodiment can be used to efficiently (specifically, for example, under milder reaction conditions within a short time) produce, for example, a polycarbonate diol or a polyester.
• the amount of the transesterification catalyst used in the present embodiment is as follows.
• the amount of the transesterification catalyst A1 is preferably 0.5 ppm or more and 20 ppm or less, more preferably 1 ppm or more and 10 ppm or less, further preferably 2 ppm or more and 7 ppm or less in terms of the total amount of the metal (M1) based on the total amount of the whole dihydroxy compound and carbonate ester
• the amount of the transesterification catalyst A2 is preferably 0.25 ppm or more and 10 ppm or less, more preferably 0.5 ppm or more and 5 ppm or less, further preferably 1 ppm or more and 3 ppm or less in terms of the total amount of the metal (M2) based on the total amount of the whole dihydroxy compound and carbonate ester.
• the reaction rate of transesterification tends to be higher.
• the amount of the transesterification catalyst is 20 ppm or less in terms of the total amount of the metal (M1), the resulting polycarbonate diol can be inhibited from being colored, and when the polycarbonate diol is used as a starting material for urethane, urethanization reaction tends to be stabilized and the resulting urethane tends to be improved in color tone and enhanced in heat resistance.
• the reaction rate of transesterification tends to be higher.
• the amount of the transesterification catalyst is 10 ppm or less in terms of the total amount of the metal (M2), the resulting polycarbonate diol can be inhibited from being colored and is smaller in ether linkage, and when the polycarbonate diol is used as a starting material for urethane, urethanization reaction tends to be stabilized and the resulting urethane tends to be improved in color tone and enhanced in heat resistance.
• a polycarbonate diol is produced by transesterification of one or a plurality of the above dihydroxy compounds and one or two or more of the above carbonate esters, in the presence of the at least two transesterification catalysts A1 and A2.
• the method for loading starting materials for the reaction is not particularly restricted, and can be freely selected from, for example, a method including loading the entire amount of one or a plurality of such dihydroxy compounds, the carbonate ester, and the catalyst at the same time and subjecting them to reaction, a method including first loading, warming and melting the carbonate ester and thereafter adding a dihydroxy compound and the catalyst in a case where the carbonate ester is a solid, and a method including first loading and melting the dihydroxy compound and then adding the carbonate ester and the catalyst thereto in contrast in a case where the dihydroxy compound is a solid.
• the reaction temperature adopted in transesterification reaction can be any temperature as long as such any temperature is a temperature providing a practical reaction rate.
• the temperature is not particularly limited, and the lower limit is preferably 80° C., more preferably 110° C., further preferably 130° C.
• the upper limit of the reaction temperature is preferably 220° C., more preferably 200° C., further preferably 180° C., particularly preferably 170° C.
• the reaction temperature is equal to or more than the lower limit, transesterification reaction tends to progress at a practical rate.
• the reaction temperature is equal to or less than the upper limit, the resulting polycarbonate diol can be inhibited from being colored, resulting in a tendency to suppress generation of ether linkage or enhance the quality, for example, improve the haze.
• the method for producing a polycarbonate diol of the present embodiment can efficiently provide a polycarbonate diol within a short time even at a low temperature of, for example, 160° C. or less (preferably 150° C. or less) under mild reaction conditions, by use of at least two transesterification catalysts A1 and A2 each containing a specified metal.
• reaction can also be performed at normal pressure
• transesterification reaction is equilibrium reaction and a monohydroxy compound or dihydroxy compound produced can be distilled off out of the system to bias the reaction to the production system.
• the reaction is usually preferably performed in the latter part thereof with such a monohydroxy compound or dihydroxy compound being distilled off under a reduced pressure condition adopted.
• the reaction can also be performed in the middle thereof with such a monohydroxy compound or dihydroxy compound produced being distilled off at a pressure being gradually reduced.
• a low-boiling point unreacted monomer can be inhibited from being volatilized, not only to result in an enhancement in yield, but also to result in a tendency to provide a polycarbonate diol having a predetermined molecular weight, or provide a polycarbonate diol having a predetermined compositional ratio in copolymerization in the case of copolymerization.
• the pressure in the reaction is appropriately selected depending on the type of a carbonate ester-derived alcohol to be distilled out, and, for example, when the alcohol to be distilled out is an alcohol having a relatively low boiling point, such as methanol, a preferred pressure in a reactor is 5 kPa to normal pressure, more preferably 7 kPa to 15 kPa. When the alcohol to be distilled out is an alcohol having a relatively high boiling point, such as ethylene glycol, a preferred pressure in a reactor is 1 to 10 kPa, more preferably 3 kPa to 7 kPa.
• the reactor can also be provided with a rectification column having a number of theoretical stages of 10 stages or more, preferably 15 stages or more, further preferably 20 stages or more, thereby efficiently separating and distilling off a monohydroxy compound or a dihydroxy compound produced from a carbonate ester by the reaction, with refluxing and separating the carbonate ester and the dihydroxy compound as the starting materials which are azeotropic.
• a rectification column having a number of theoretical stages of 10 stages or more, preferably 15 stages or more, further preferably 20 stages or more, thereby efficiently separating and distilling off a monohydroxy compound or a dihydroxy compound produced from a carbonate ester by the reaction, with refluxing and separating the carbonate ester and the dihydroxy compound as the starting materials which are azeotropic.
• a rectification column having a number of theoretical stages of 10 stages or more, preferably 15 stages or more, further preferably 20 stages or more, thereby efficiently separating and distilling off a monohydroxy compound or a dihydroxy compound produced
• the reaction is usually preferably performed at an increased degree of pressure reduction with switching to simple distillation in the end phase of the reaction because a monohydroxy compound or a dihydroxy compound as a by-product, such as alcohol and diol, and phenol, the remaining monomer such as the carbonate ester, and furthermore cyclic carbonate (cyclic oligomer) capable of causing clouding can be efficiently distilled off.
• a monohydroxy compound or a dihydroxy compound as a by-product such as alcohol and diol, and phenol
• the remaining monomer such as the carbonate ester, and furthermore cyclic carbonate (cyclic oligomer) capable of causing clouding
• the reaction pressure at the end of the reaction is not particularly limited, and the upper limit is usually preferably 5 kPa, more preferably 2 kPa, further preferably 1 kPa or less.
• the reaction can also be performed with a small amount of an inert gas such as nitrogen, argon, or helium being allowed to pass in order to effectively distill off such a low-boiling point content.
• polymerization reaction (polycondensation reaction) can be performed in a batch manner or in a continuous manner, such reaction is more excellently performed in a continuous manner in terms of stability of quality such as the molecular weight of a product.
• the apparatus used may be in any form of tank, tube and column types, and a known polymerization tank or the like equipped with various stirring blades can be used.
• the atmosphere during temperature rise of the apparatus is not particularly restricted, and the reaction is preferably performed in an inert gas such as a nitrogen gas under normal pressure or reduced pressure from the viewpoint of the quality of a product.
• the reaction time necessary for achieving a predetermined molecular weight is usually preferably 20 hours or less, more preferably 10 hours or less, further preferably 5 hours or less.
• the transesterification catalyst or its residue may usually remain in the resulting polycarbonate diol not to allow for control of polyurethanization reaction being performed.
• a catalyst deactivator for example, a phosphorus-based or sulfur-based compound which is acidic or is decomposed and then made acidic may be added in an almost equimolar amount to that of the transesterification catalyst used.
• a heating treatment described below can be conducted to efficiently deactivate the transesterification catalyst. Such deactivation can decrease color formation derived from the transesterification catalyst, and the polycarbonate diol can achieve a Hazen color index of preferably 50 or less, more preferably 30 or less, as measured according to JIS-K0071-1 (1998).
• the catalyst deactivator can be added to suppress coloration and the changes in physical properties, which are caused due to the changes in terminal structures and backbones of the polycarbonate diol and the remaining catalyst during storage and handling of the resulting polycarbonate diol composition at a high temperature for a long time.
• Examples of a compound (hereinafter, sometimes referred to as “catalyst deactivator”) used for deactivation of the transesterification catalyst include, but not particularly limited, inorganic phosphoric acids such as phosphoric acid and phosphorus acid, organic phosphate esters such as monobutyl phosphate, dibutyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate and triphenyl phosphite, and sulfonic acid and sulfonate ester. These may be used singly or in combinations of two or more kinds thereof.
• inorganic phosphoric acids such as phosphoric acid and phosphorus acid
• organic phosphate esters such as monobutyl phosphate, dibutyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate and triphenyl phosphite
• the amount of the catalyst deactivator used is not particularly limited and may be an almost equimolar amount to that of the transesterification catalyst used, as described above, and specifically, the upper limit is preferably 5 mol, more preferably 2 mol, and the lower limit is preferably 0.8 mol, more preferably 1.0 mol, based on 1 mol of the transesterification catalyst used.
• the catalyst deactivator is used in an amount equal to or more than the lower limit, the transesterification catalyst in the reaction product is sufficiently deactivated, and the resulting polycarbonate diol, when used as a starting material for polyurethane production, tends to be able to have a sufficiently reduced reactivity with an isocyanate group.
• the resulting polycarbonate diol tends to not only be able to be suppressed in coloration, but also be able to favorably promote polymerization of urethane when used as a starting material for urethane.
• the deactivation of the transesterification catalyst by addition of the catalyst deactivator can be made even at room temperature, but is more efficiently made by a heating treatment.
• the temperature of such a heating treatment is not particularly limited, the upper limit is preferably 140° C., more preferably 130° C., further preferably 120° C., and the lower limit is preferably 80° C., more preferably 100° C., further preferably 110° C.
• a temperature equal to or more than the lower limit allows the time for deactivation of the transesterification catalyst to be shortened and thus is efficient, and also allows for a sufficient degree of deactivation.
• a phosphorus-based compound is used as the deactivator, a temperature of 140° C.
• the resulting polycarbonate diol can be suppressed in coloration, and tends to allow for stable urethanization reaction when used as a starting material for urethane.
• the time for reaction with the catalyst deactivator is not particularly limited, and is, for example, 1 to 5 hours.
• the polycarbonate diol of the present embodiment satisfies the following formula (A):
• R represents a divalent aliphatic hydrocarbon group or alicyclic hydrocarbon group having 2 to 20 carbon atoms
• m is an integer of 2 or more and 600 or less.
• R preferably represents a divalent aliphatic hydrocarbon group or alicyclic hydrocarbon group having 2 to 20 carbon atoms.
• R examples include, but not particularly limited, propylene, tetramethylene, pentamethylene, hexamethylene, nonamethylene, decamethylene, 2,2-dimethyl-1,3-propylene, 2-methyl-1,3-propylene, 3-methyl-pentamethylene, and 2-methyl-octamethylene
• specific examples of the alicyclic hydrocarbon group include 1,4-cyclohexanedimethylene and tricyclodecanedimethylene, and in particular, propylene, tetramethylene, pentamethylene, and hexamethylene are preferred.
• m is preferably an integer of 2 to 600, more preferably an integer of 3 to 100, further preferably an integer of 5 to 30.
• the polycarbonate diol of the present embodiment is preferably a polycondensation product by the transesterification reaction of the dihydroxy compound and the carbonate ester.
• the lower limit of the number average molecular weight (Mn) of the polycarbonate diol of the present embodiment is 250, preferably 500, more preferably 750, further preferably 1000.
• the upper limit of the number average molecular weight (Mn) of the polycarbonate diol of the present embodiment is 100000, preferably 50000, further preferably 10000, particularly preferably 3000.
• the number average molecular weight of the polycarbonate diol is equal to or more than the lower limit, a polyurethane formed tends to be improved in, for example, flexibility.
• the number average molecular weight of the polycarbonate diol is equal to or less than the upper limit, the polycarbonate diol is reduced in viscosity and tends to be easily handled during polyurethanization.
• the number average molecular weight of the polycarbonate diol is determined from the hydroxyl value (average hydroxyl valence) of the polycarbonate diol, as shown in Examples described below.
• Examples of the method for controlling the number average molecular weight (Mn) of the polycarbonate diol within the above range include, but not particularly limited, a method including adjusting the polycondensation reaction time of the polycarbonate diol and adjusting the amount of the dihydroxy compound as a starting material monomer to be extracted, to control the number average molecular weight (Mn) of the polycarbonate diol within the above range.
• the color of the polycarbonate diol of the present embodiment is preferably 50 or less, more preferably 40 or less, further preferably 30 or less, particularly preferably 20 or less as the value (hereinafter, designated as “APHA value”.) expressed by the Hazen color index (according to JIS K0071-1:1998).
• the lower limit of the APHA value is not particularly limited, and is, for example, 0 or more.
• Examples of the method for controlling the APHA value of the polycarbonate diol within the above range include, but not particularly limited, a method including performing the transesterification reaction at a reaction temperature falling within a preferred temperature range described above and a method including performing the transesterification reaction (polymerization reaction or polycondensation reaction) for a required time for the reaction, within a preferred temperature range described above.
• the APHA value of the polycarbonate diol can be measured by a method described in Examples below.
• the polycarbonate diol of the present embodiment preferably includes at least one metal (M1) selected from the group consisting of metals in Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 in the long-period type periodic table and at least one metal (M2) selected from the group consisting of metals in Group 1 and Group 4 in the long-period type periodic table, as metals contained.
• M1 selected from the group consisting of metals in Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 in the long-period type periodic table
• M2 selected from the group consisting of metals in Group 1 and Group 4 in the long-period type periodic table, as metals contained.
• the polycarbonate diol of the present embodiment preferably contains at least one metal (M1) selected from the group consisting of metals in Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 in the long-period type periodic table in a total amount of 1 ppm or more and 25 ppm or less, more preferably 2 ppm or more and 15 ppm or less, further preferably 5 ppm or more and 10 ppm or less.
• M1 metal selected from the group consisting of metals in Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 in the long-period type periodic table in a total amount of 1 ppm or more and 25 ppm or less, more preferably 2 ppm or more and 15 ppm or less, further preferably 5 ppm or more and 10 ppm or less.
• the polycarbonate diol of the present embodiment when contains the metal (M1) at a content of 1 ppm or more in terms of the total amount thereof, is reduced in APHA value, and tends to result in an enhancement in reaction rate of urethanization when used as a starting material for urethane.
• the polycarbonate diol of the present embodiment when contains the metal (M1) at a content of 25 ppm or less in terms of the total amount thereof, can be inhibited from being colored due to heating, and tends to allow for stable urethanization reaction when used as a starting material for urethane.
• the metal (M1) contained in the polycarbonate diol of the present embodiment is preferably at least one metal selected from the group consisting of molybdenum, manganese, iron, cobalt, nickel and copper. Among them, in particular, manganese is more preferred.
• Such a metal contained in the polycarbonate diol may be present as a residue of the polymerization catalyst, or may be added in a predetermined amount intendedly after production.
• the polycarbonate diol of the present embodiment preferably contains at least one metal (M2) selected from the group consisting of metals in Group 1 and Group 4 in the long-period type periodic table in a total amount of 0.5 ppm or more and 12.5 ppm or less, more preferably 0.7 ppm or more and 7.5 ppm or less, further preferably 1 ppm or more and 3 ppm or less.
• M2 metal selected from the group consisting of metals in Group 1 and Group 4 in the long-period type periodic table in a total amount of 0.5 ppm or more and 12.5 ppm or less, more preferably 0.7 ppm or more and 7.5 ppm or less, further preferably 1 ppm or more and 3 ppm or less.
• the polycarbonate diol of the present embodiment when contains the metal (M2) at a content of 0.5 ppm or more in terms of the total amount thereof, is reduced in APHA value, and tends to result in an enhancement in reaction rate of urethanization when used as a starting material for urethane.
• the polycarbonate diol of the present embodiment when contains the metal (M2) at a content of 12.5 ppm or less in terms of the total amount thereof, is decreased in amount of ether linkage and can be inhibited from being colored due to heating, and tends to allow for stable urethanization reaction when used as a starting material for urethane.
• Such a metal contained in the polycarbonate diol may be present as a residue of the polymerization catalyst, or may be added in a predetermined amount intendedly after production.
• the polycarbonate diol of the present embodiment has a basic structure in which a dihydroxy compound is polymerized by a carbonate group.
• ether linkage resulting from any side reaction such as partial dehydration of the dihydroxy compound and/or partial decarboxylation reaction of the carbonate ester may be incorporated depending on the production method, and the amount of presence thereof may be increased to result in deterioration in weather resistance and/or heat resistance and therefore production is preferably made so that the proportion of the ether linkage is not excessively high.
• the amount of the ether linkage contained in a molecular chain of the polycarbonate diol of the present embodiment is usually 5% by mol or less, preferably 3% by mol or less, more preferably 2% by mol or less in terms of percent by mol.
• a value can be determined by alkali hydrolysis and gas chromatographic measurement. Specifically, such a value can be measured by a method described in Examples below.
• Examples of the method for controlling the amount of the ether linkage contained in the polycarbonate diol include, but not particularly limited, a method including production with the transesterification catalyst of the present application under milder reaction conditions within a short time.
• the terminal primary hydroxyl group (OH) purity of the polycarbonate diol of the present embodiment is preferably 97% or more, more preferably 98% or more, further preferably 99% or more.
• the reaction rate in production (synthesis) of a polyurethane (in particular, thermoplastic polyurethane) with the polycarbonate diol of the present embodiment as a starting material compound tends to be increased, and the resulting polyurethane tends to be high in strength.
• the above transesterification catalysts A1 and A2 can be used to shorten the reaction time and also produce the polycarbonate diol under mild reaction conditions, and therefore a high terminal primary hydroxyl group (OH) purity can be achieved.
• the terminal primary hydroxyl group (OH) purity of the polycarbonate diol can be measured by a method described in Examples below.
• the polycarbonate diol of the present embodiment is excellent in mechanical properties and durability, and therefore can be used in various applications.
• the polycarbonate diol can be widely used for foam, elastomers, coating materials, fibers, adhesives, floor materials, sealants, medical materials, artificial leather, coating agents, aqueous polyurethane coating materials, and the like.
• the polycarbonate diol of the present embodiment when used as a starting material particularly in applications of artificial leather, synthetic leather, aqueous polyurethane, adhesives, medical materials, floor materials, coating agents, and the like, can impart good surface properties where excellent weather resistance, heat resistance, moisture and heat resistance, and friction resistance are excellent to cause less coloration, hardly cause scratches due to scratching or the like, and cause less degradation due to friction, and therefore can be suitably used as a starting material for various coatings.
• a polyurethane of the present embodiment includes the above polycarbonate diol.
• the polyurethane of the present embodiment includes the above polycarbonate diol and therefore is excellent in chemical resistance, heat resistance, and hydrolysis resistance.
• a carbonate ester for example, ethylene carbonate (EC)
• a dihydroxy compound starting material diol
• PCD polycarbonate diol
• a carbonate ester-derived hydroxy compound a monohydroxy compound in the case of dialkyl carbonate as a starting material carbonate ester, or a dihydroxy compound in the case of alkylene carbonate as a starting material carbonate ester, for example, ethylene glycol (EG)
• EG ethylene glycol
• ethylene carbonate (EC) as the carbonate ester
• ethylene glycol (EG) is produced as a by-product by the reaction.
• a method for evaluating catalyst performance involved determining the amount of a hydroxy compound (a monohydroxy compound in the case of dialkyl carbonate as a starting material carbonate ester, or a dihydroxy compound in the case of alkylene carbonate as a starting material carbonate ester, for example, ethylene glycol (EG)) distilled out each after 1 hour and 2 hours from reaction initiation in generation reaction of a polycarbonate diol (PCD) from a dihydroxy compound and a carbonate ester, according to gas chromatography, and determining the carbonate conversion according to the following expression (15), (16) or (17).
• a hydroxy compound a monohydroxy compound in the case of dialkyl carbonate as a starting material carbonate ester, or a dihydroxy compound in the case of alkylene carbonate as a starting material carbonate ester, for example, ethylene glycol (EG)
• PCD polycarbonate diol
• Carbonate ⁇ conversion ⁇ ( % ) ( Number ⁇ of ⁇ moles ⁇ of ⁇ dihydroxy ⁇ compound ⁇ distilled ⁇ out ) / ( Number ⁇ of ⁇ moles ⁇ of ⁇ carbonate ⁇ ester ⁇ loaded ) ⁇ 100 ( 15 )
• Carbonate ⁇ conversion ⁇ ( % ) ( Number ⁇ of ⁇ moles ⁇ of ⁇ hydroxy ⁇ compound ⁇ distilled ⁇ out / 2 ) / ( Number ⁇ of ⁇ moles ⁇ of ⁇ carbonate ⁇ ester ⁇ loaded ) ⁇ 100 ( 16 )
• Carbonate ⁇ conversion ⁇ ( % ) ( Number ⁇ of ⁇ moles ⁇ of ⁇ phenol ⁇ distilled ⁇ out / 2 ) / ( Number ⁇ of ⁇ moles ⁇ of ⁇ carbonate ⁇ ester ⁇ loaded ) ⁇ 100 ( 17 )
• the reaction rate in polyester diol synthesis was determined from the amount of an alcohol (for example, methanol in the case of dibasic acid dimethyl ester as a starting material) distilled off by the reaction, according to the following expression (17)′.
• an alcohol for example, methanol in the case of dibasic acid dimethyl ester as a starting material
• reaction ⁇ rate ( Number ⁇ of ⁇ moles ⁇ of ⁇ alcohol ⁇ distilled ⁇ out / 2 ) / ⁇ ( Number ⁇ of ⁇ moles ⁇ of ⁇ dibasic ⁇ acid ⁇ ester ⁇ loaded ) ⁇ 100 ( 17 ) ′
• An acetylation reagent was prepared by diluting 12.5 g of acetic anhydride with 50 mL of pyridine in a measuring flask. In a 100-mL round-bottom flask was precisely weighed 2.5 to 5.0 g of a sample. After 5 mL of an acetylation reagent and 10 mL of toluene were added through a whole pipette to the round-bottom flask, a cooling tube was mounted and the solution in the round-bottom flask was stirred and heated at 100° C. for 1 hour.
• a blank test was made by placing 5 mL of an acetylation reagent, 10 mL of toluene, and 2.5 mL of distilled water in a 100-mL round-bottom flask, heating and stirring them for 10 minutes, and then performing titration in the same manner as described above. The results were used to calculate the OH value according to the following expression (18).
• the number average molecular weight was determined by the following expression (19).
• the Hazen color index was measured by comparison with a standard liquid placed in a colorimetric tube, according to JIS K0071-1.
• the polycarbonate diol which was a solid at normal temperature was warmed to 70° C. and molten, and then subjected to measurement of the Hazen color index (APHA value).
• GC analysis was performed with gas chromatography GC-14B (manufactured by Shimadzu Corporation, Japan) equipped with DB-WAX (manufactured by Agilent J&W, USA) as a column, 1,3-propanediol as an internal standard, and a hydrogen flame ionization detector (FID) as a detector, and each component was quantitatively analyzed.
• the temperature rise profile of the column was a profile including retention at 100° C. for 5 minutes and then temperature rise to 200° C. at 5° C./min.
• the ether linkage is considered to be generated by dehydration reaction of a hydroxyl group or decomposition (decarboxylation) of a carbonate ester, and, for example, in a case where a polycarbonate diol is produced with ethylene carbonate and hexanediol as starting materials, diethylene glycol and 6-(2-hydroxyethoxy) hexane-1-ol are detected as compounds with ether linkage.
• GC analysis gas chromatographic analysis
• OH terminal primary hydroxyl group
• % of the polycarbonate diol was calculated from the value of the peak area in the resulting chromatograph, according to the following expression (20).
• GC analysis was performed with gas chromatography 6890 (manufactured by Hewlett-Packard Company, USA) equipped with 30-m DB-WAX (manufactured by Agilent J&W, USA) having a membrane thickness of 0.25 ⁇ m, as a column, and a hydrogen flame ionization detector (FID) as a detector.
• the temperature rise profile of the column was a profile of temperature rise from 60° C. to 250° C. at 10° C./min and then retention at that temperature for 15 minutes.
• the GC apparatus used was 6890 (manufactured by Hewlett-Packard Company, USA) equipped with DB-WAX (manufactured by Agilent J&W, USA) as a column.
• the temperature was raised from an initial temperature of 40° C. to 220° C. at a rate of temperature rise of 10° C./min in the GC apparatus.
• the MS apparatus used was Auto-mass SUN (manufactured by JEOL Ltd.). In the MS apparatus, the ionization voltage was 70 eV, the scanning range m/z was 10 to 500, and the photomultiplier gain was 450 V.
• Terminal ⁇ primary ⁇ OH ⁇ ratio ⁇ ( % ) B / A ⁇ 100 ( 20 )
• the metal ion concentration in acetonitrile used as a solvent was measured as a blank value, and the value obtained by subtracting the metal ion concentration in this solvent content from the metal ion concentration in the above solution diluted was defined as the metal ion concentration in the polycarbonate diol product. Measurement conditions were as shown below. The calibration curves of various metals, created in advance, were used to determine the concentrations of such various metals remaining in the polycarbonate diol.
• N, N-dimethylacetamide (DMF) solution was prepared so that the polyurethane concentration was 0.1% by mass.
• the DMF solution prepared was used to measure each molecular weight of polyurethane, as follows.
• a GPC apparatus [product name “HLC-8320” (column: Tskgel Super HM-H ⁇ 4) manufactured by Tosoh Corporation] was used in the measurement.
• the eluent used was a solution in which 2.6 g of lithium bromide was dissolved in 1 L of dimethylacetamide.
• Mn number average molecular weight
• a strip-shaped test piece having a width of 10 mm, a length of 100 mm, and a thickness of about 0.5 mm was produced from a polyurethane film, according to JIS K6301 (2010).
• a tensile test of the test piece produced was carried out with a tensile tester (product name “Tensilon, Model RTE-1210” manufactured by Orientec Corporation) at a distance between chucks of 20 mm and a tensile speed of 100 mm/min and at a temperature of 23° C. (relative humidity 55%).
• the test piece was measured with respect to the stress at the time of 100% elongation (100% modulus), the strength at breaking, and the elongation at breaking.
• a test piece of 3 cm ⁇ 3 cm was cut out from a polyurethane film.
• a strip-shaped test piece having a width of 10 mm, a length of 100 mm, and a thickness of about 50 ⁇ m was produced from a polyurethane film.
• the test piece was heated in a gear oven at a temperature of 120° C. for 1000 hours.
• the breaking strength of the test piece after heating was measured in the same manner as in the above [Tensile test at room temperature].
• the breaking strength retention rate (%) was determined by the following expression.
• Breaking ⁇ strength ⁇ retention ⁇ rate ⁇ ( % ) Breaking ⁇ strength ⁇ of ⁇ test ⁇ piece ⁇ after ⁇ heating / Breaking ⁇ strength ⁇ of ⁇ test ⁇ piece ⁇ before ⁇ test ⁇ 100
• a strip-shaped test piece having a width of 10 mm, a length of 100 mm, and a thickness of about 50 ⁇ m was produced from a polyurethane film.
• the test piece was heated in a constant temperature and humidity bath at a temperature of 85° C. and a relative humidity of 85% for 200 hours.
• the breaking strength of the test piece after heating was measured in the same manner as in the above [Tensile test at room temperature].
• the breaking strength retention rate (%) was determined by the following expression.
• Breaking ⁇ strength ⁇ retention ⁇ rate ⁇ ( % ) Breaking ⁇ strength ⁇ of ⁇ test ⁇ piece ⁇ after ⁇ heating / Breaking ⁇ strength ⁇ of ⁇ test ⁇ piece ⁇ before ⁇ test ⁇ 100
• a 1-L separable flask equipped with a stirring machine, a thermometer and an Oldershaw (number of theoretical stages of 15) with a vacuum jacket having a reflux head at the top of head were loaded with 355 g (3.00 mol) of 1,6-hexanediol and 264 g (3.00 mol) of ethylene carbonate as starting material monomers, and 16.3 mg of Mn(acac) 2 ⁇ 2H 2 O and 6.7 mg of Li—OMe were added as catalysts.
• the starting materials in the flask were heated in an oil bath set to 170° C., and such starting material monomers were polycondensed by transesterification reaction for 2 hours with one portion of a fraction being extracted through the reflux head at an inner temperature of the flask of 150° C. and a degree of vacuum of 4 kPa, thereby obtaining a polycarbonate diol.
• the carbonate conversion was analyzed by gas chromatography after 1 hour and 2 hours from reaction initiation. The amount of ether linkage after 2 hours from reaction initiation was also measured. The results were shown in Table 1.
• Each polycarbonate diol was obtained by polycondensation of starting material monomers by transesterification reaction in the same manner as in Example 1 except that the types and amounts of the catalysts added were those described in Table 1.
• the carbonate conversion was analyzed by gas chromatography after 1 hour and 2 hours from reaction initiation in the same manner as in Example 1.
• the amount of ether linkage after 2 hours from reaction initiation was also measured. The results were shown in Table 1.
• a 1-L separable flask equipped with a stirring machine, a thermometer and an Oldershaw (number of theoretical stages of 15) with a vacuum jacket having a reflux head at the top of head were loaded with 523 g (3.00 mol) of dimethyl adipate and 1,4-butanediol 270 g of (3.00 mol) as starting material monomers, and 17.7 mg of Mn(OAc) 2 ⁇ 4H 2 O and 8.6 mg of Li—OMe were added as catalysts.
• the starting materials in the flask were heated in an oil bath set to 170° C., and such starting material monomers were polycondensed by transesterification reaction for 2 hours with one portion of a fraction being extracted through the reflux head at an inner temperature of the flask of 150° C. and normal pressure, thereby obtaining a polyester diol.
• the carbonate conversion was analyzed by gas chromatography after 1 hour and 2 hours from reaction initiation. The results were shown in Table 1-1.
• Each polycarbonate diol was obtained by polycondensation of starting material monomers by transesterification reaction in the same manner as in Example 1A except that the types and amounts of the catalysts added were those described in Table 1-1.
• the carbonate conversion was analyzed by gas chromatography after 1 hour and 2 hours from reaction initiation in the same manner as in Example 1A. The results were shown in Table 1-1.
• Each polycarbonate diol was obtained by polycondensation of starting material monomers by transesterification reaction in the same manner as in Example 1 except that the types and amounts of catalysts added were those described in Table 2 and the reaction temperature was each temperature described in Table 2.
• the carbonate conversion was analyzed by gas chromatography after 1 hour and 2 hours from reaction initiation in the same manner as in Example 1.
• the amount of ether linkage after 2 hours from reaction initiation and the APHA were also measured. The results were shown in Table 2.
• Each polycarbonate diol was obtained by polycondensation of starting material monomers by transesterification reaction in the same manner as in Example 1 except that the types and amounts of the catalysts added and the type of the carbonate ester used was as described in Table 3.
• the carbonate conversion was analyzed by gas chromatography after 1 hour and 2 hours from reaction initiation in the same manner as in Example 1. The results were shown in Table 3.
• Each polycarbonate diol was obtained by polycondensation of starting material monomers by transesterification reaction in the same manner as in Example 1 except that the types and amounts of catalysts added and the type and amount of the dihydroxy compound used were those described in Table 4.
• the carbonate conversion was analyzed by gas chromatography after 1 hour and 2 hours from reaction initiation in the same manner as in Example 1. The results were shown in Table 4.
• a 1-L separable flask equipped with a stirring machine, a thermometer and an Oldershaw (number of theoretical stages of 15) with a vacuum jacket having a reflux head at the top of head were loaded with 355 g (3.00 mol) of 1,6-hexanediol and 264 g (3.00 mol) of ethylene carbonate, and 13.8 mg of Mn(OAc) 2 ⁇ 4H 2 O and 6.7 mg of Li—OMe were added as catalysts.
• the starting materials in the flask were heated in an oil bath set to 170° C., and such starting material monomers were polycondensed by transesterification reaction for 2 hours with one portion of a fraction being extracted through the reflux head at an inner temperature of the flask of 150° C. and a degree of vacuum of 4 kPa, thereby obtaining a polycarbonate diol.
• the carbonate conversion here (after 2 hours from reaction initiation) was measured. The measurement results are shown in Table 5.
• Each polycarbonate diol was obtained by polycondensation of starting material monomers by transesterification reaction in the same manner as in Example 38 except that the type and amount of the dihydroxy compound used were those described in Table 5.
• the carbonate conversion after 2 hours from reaction initiation and properties of the polycarbonate diol obtained were shown in Table 5.
• the resulting polycarbonate diols are respectively referred to as PC2, PC3, and PC4.
• a polycarbonate diol was obtained by polycondensation of starting material monomers by transesterification reaction in the same manner as in Example 41 except that the type and amount of the dihydroxy compound used were those described in Table 5 and the reaction time after switching to simple distillation was 0.5 hours.
• the carbonate conversion after 2 hours from reaction initiation and properties of the polycarbonate diol obtained were shown in Table 5.
• the resulting polycarbonate diol is referred to as PC5.
• a polycarbonate diol was obtained by polycondensation of starting material monomers by transesterification reaction in the same manner as in Example 41 except that the type and amount of the dihydroxy compound used were those described in Table 5 and the reaction time after switching to simple distillation was 2 hours.
• the carbonate conversion after 2 hours from reaction initiation and properties of the polycarbonate diol obtained were shown in Table 5.
• the resulting polycarbonate diol is referred to as PC6.
• a 1-L separable flask equipped with a stirring machine, a thermometer and an Oldershaw (number of theoretical stages of 15) with a vacuum jacket having a reflux head at the top of head were loaded with 156 g of 1,5-pentanediol, 177 g of 1,6-hexanediol, and 264 g (3.00 mol) of ethylene carbonate as starting material monomers, and 13.8 mg of Mn(OAc) 2 ⁇ 4H 2 O was added as a catalyst.
• the starting materials in the flask were heated in an oil bath set to 170° C., and reacted for 7 hours with one portion of a fraction being extracted through the reflux head at an inner temperature of the flask of 150° C.
• Monobutyl phosphate as a catalyst deactivator was loaded in an equimolar amount to the amount of the catalysts loaded, and stirred at a temperature of 110 to 120° C. for 3 hours.
• the results of analysis of the resulting polycarbonate diol are shown in Table 5.
• the polycarbonate diol is referred to as PC7.
• a 1-L separable flask equipped with a stirring machine, a thermometer and an Oldershaw (number of theoretical stages of 15) with a vacuum jacket having a reflux head at the top of head were loaded with 156 g of 1,5-pentanediol, 177 g of 1,6-hexanediol, and 264 g (3.00 mol) of ethylene carbonate as starting material monomers, and 6.7 mg of Li—OMe was added as a catalyst.
• the starting materials in the flask were heated in an oil bath set to 170° C., and reacted for 7 hours with one portion of a fraction being extracted through the reflux head at an inner temperature of the flask of 150° C. and a degree of vacuum of 4 kPa.
• Monobutyl phosphate as a catalyst deactivator was loaded in an equimolar amount to the amount of the catalysts loaded, and stirred at a temperature of 110 to 120° C. for 3 hours.
• the results of analysis of the resulting polycarbonate diol are shown in Table 5.
• the polycarbonate diol is referred to as PC8.
• a polycarbonate diol was obtained by polycondensation of starting material monomers by transesterification reaction in the same manner as in Comparative Example 9 except that the amount of Li—OMe was 33.5 mg.
• the carbonate conversion after 2 hours from reaction initiation and properties of the polycarbonate diol obtained were shown in Table 5.
• the resulting polycarbonate diol is referred to as PC9.
• MDI diphenylmethane-4,4′-diisocyanate
• DMF N, N-dimethylformamide
• the solution obtained was continued to be stirred for 1 hour, and thereafter 3.2 g of 1,4-butanediol (hereinafter, also designated as “14BDO”) was added. After the solution was stirred at 60° C. for additional 3 hours, 1 g of ethyl alcohol was added to stop the reaction.
• the resulting polyurethane solution was applied onto a polypropylene resin sheet (width 100 mm, length 1200 mm, thickness 1 mm) with an applicator so that the width was 80 mm, the length was 100 mm and the thickness was 0.6 mm, and thus a coating film was obtained.
• the coating film obtained was dried on a hot plate having a surface temperature of 60° C., for 2 hours, and subsequently dried in an oven at 100° C.
• the coating film was left to still stand under a constant temperature of 23° C. and a constant humidity of 55% RH for 48 hours or more, and thus a polyurethane film was obtained.
• the polyurethane film obtained was subjected to evaluations of various physical properties. The evaluation results were shown in Table 6.
• Each polyurethane film was obtained in the same manner as in Example 44 except that PC2 to PC9 were each used as the polycarbonate diol and the amounts of MDI and 14BDO were amounts shown in Table 6.
• the polyurethane films obtained were subjected to evaluations of various physical properties. The evaluation results were shown in Table 6.
• Japanese Patent Application Japanese Patent Application No. 2022-005675 filed on Jan. 18, 2022 and Japanese Patent Application (Japanese Patent Application No. 2022-109959) filed on Jul. 7, 2022, the contents of which are herein incorporated by reference.

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